Destructive hydrogenation of carbonaceous materials



April 1o, 1934.

DESTRUCTIVE HYDROGENATIYON OF CARBONACEOUSKMATERIALS M. PIER ET AL yFiled April 25, 1929 BY M12/W A TTORNEYS.

4UNITED STATES lm'rrzN'r; OFFICE DESTRUCTIVE' HYDBOGENATION 0F CABBONACEQUS MATERIALS Mathias Pier, Heidelberg, and Kurt Wissel, Ludwgshafen-on-the-Rhine, Germany, assignors, by mesne assignments, to Standard-I. G. Company, Linden, N. J., a corporation'of Delaware Application April 25, 1929, Serial No. 358,154 In Germany June 18, 1928 5 claims. (c1. 19e- 53) This invention relates to an improved method hydrocarbons which have not been removed by for the recovery of the valuable low-boiling prodthe liquid products obtained in the reaction itucts and in particular of the gaseous products self. present in the reaction mixture obtained from As a rule the products issuing from the destruc- 5 processes for the destructive hydrogenation of I tive hydrogenation are cooled to about room o distillable carbonaceous materials. temperature. It is', however,to be understood We have found that in the destructive hydrothat also other cooling temperatures, for example genation under pressure of distillable carbon- 20 or 30 above or below ordinary temperature, aceous materials, such as coal in all its varieties, may be employed. In thesecases the compositars, mineral oils, the products obtained lfrom tion of the nal liquids obtained will be somethe said substances by distillation, extraction or what different from that resulting at ordinary conversion and the like for the purpose of protemperature. Also the composition of. the unducing valuable liquid products such as bencondensed gases and the gases obtained after zines, lubricating oils and the like, other valuable each stage of pressure release will differ from low-boiling and in particular gaseous products that of the corresponding` gases obtained by 70 are obtained by subjecting to condensation, while cooling to ordinary temperature. In any case, still under pressure, the gases and vapors leaving however, gases containing hydrogen and hydrothe reaction chamber, separating the unconcarbons of low boiling points, in particular gasdensed gases and vapors from the condensate eous hydrocarbons, are obtained. Since the said o obtained and then fractionally releasing the gases, before being used for' the hydrogenation pressure on the said condensate. The said process, are ordinarily removed from the gascondensatlon is elected by cooling.) eous hydrocarbons contained therein, for ex- The fractional releasing of pressure is of greatv ample by Washing With Oils, verydlieleni" C001- 'technical' advantage since the gas lobtained by ing temperatures may be employed. c

the nrst releasing of the pressure on the con- 'As examples 0f pressures suitable for applica;` densate, whichis very rich in hydrogen may be tion in the said destructive hydrogenation may again employed in the destructive hydrogenation be meniiened 20, 50. 100. 200 atmospheres 01 even process, preferably after removal of the small higher preSSufeS. fOr example 1000 atmospheres* quantities of hydrocarbons therein, for example The prOCeSS may be Carried 011i' inthe Presence by thermal decomposition, at temperatures of 0f catalysts, Such immune from pOiSOning by S111- say about 900 centigrade or more, or,` for in- -phur being of particular advantage, and more stance, by treatment with' steam, carbon dioxide, especially, those comprising a metal, usually in or other decomposing gases in the presence of the form of a compound from the sixth group of catalysts such'as iron or nickel for example at the periodic system. Examples of such catalysts 5 about 500 to 1200 centigrade. The gas obtained are those prepared from molecular proportions by further `releasing of the pressure contains of molybdic acid and zinc oxide-or from molecular `valuable hydrocarbons such as pentane, propane, proportions of tungstic acid,- zinc oxide and magbutane and the like in a concentrated form, and nesum oxide. When very active catalysts such as these may be isolated for example by compresthose containing molybdenum are employed, pression or by `strong cooling. A particular adsures as low as 5 atmospheres may be utilized with vantage of the fractional releasing of pressure-is advantage in the destructive hydrogenation. that the amount of hydrogen contained in the -The nature of` the present invention will be furgas obtained by the second or later stages of the ther understood with reference to the accompanyfractional releasing of pressure is very small, and ing drawing which shows in a somewhat diagramthus the los's of hydrogen from the circulating matie manner en elevation. Partly in Section, 0f

gas is reduced to a minimum. a plant suitable for carrying out the process ac- By a repeated compression of the gas obtained cordng t0 the Present invention. by releasing the pressure or by washing the same Referring to the drawing in detail numeral 1 dewith solvents and absorbents, or by both these notes e high Pressure Vessel iniiO` Which blOWn operations, a--further separation and also a con- COal tar Supplied by pipe 20 iS treated With hydro- J c densation of any hydrocarbon vapor, which has 4gen, supplied at 19, at a temperature oi 450 C. been carried along may be effected. and under a pressure of 200 atmospheres. The The hydrogenating gas which is t9 be used in liquid and vaporous products issuing from the circulation may also be subjected to washing' high pressure'vessel are passed at the same presin order to wash out any hydrogen sulphide and sure, together with the waste hydrogenating gas.

into the condenser 2 cooled with water in which the constituents `condensable at ordinary temperature are condensed. In the liquid product issuing from the condenser 2 and of which 15 per cent boil up to 200 C. and 70 per cent up to 325 C., hydrogen, methane, gaseous homologues thereof -and hydrogen sulphide are absorbed in amounts corresponding to the partial pressures thereof in the uncondensed gases. The liquids are then separated from the gases in the separating vessel 3, whereupon the liquids are conveyed through valves 4a and 4b into the vessel 5 maintained ata pressure of 25 atmospheres, The constituents remaining liquid in this vessel are then passed by way of valves 6a and 6b into vessel 'l kept at ordinary pressure wherefrom the liquids are withdrawn at 8 while the gases evolved,\ consisting of from 5 to 10 per cent of hydrogen, 'l0 to per cent of methane and gaseous homologues thereof and 5 per cent of hydrogen sulphide, are removed at 9. The gases and vapors evolved in vessel 5 are led by way of pipe 10 into washing tower 11 in which they are passed under a pressure of 25 atmospheres through a shower of washing oil supplied at 12 which adsorbs in particular the gaseous hydrocarbons and hydrogen sulphide. The waste washing oil is released from pressure by valve 13 and then separated from the gases evolved therefrom in the separating vessel 14. The washing oil withdrawn from vessel 14 may be recycled to vessel 11 by way of pump 16, if desired after adding thereto fresh washing oil supplied at 17h. The gas issuing at the top of vessel 1'1 is practically free from hydrocarbons and hydrogen sulphide. It may, after compression to 200 atmospheres in compressor 18, be recycled to the hydrogenating vessel l. The gas not condensed in the condenser^2 leaves the separating vessel 3 at 21 and is washed, while under a pressure of 200 atmospheres, in the washing tower 22 capable of resisting high pressures. The washing oil requisite for this operation is sprayed in at 23 and withdrawn at the bottom of the said tower. It is then relieved `from pressure by valves 24, whereby the gases dissolved in the oil are substantially evolved therefrom. The oil is separated from these gases in separating vessel 26 and may be returned to the washing tower 22 by way of pump 27. The gases separated in vessel 26 from the washing oil are withdrawn at 25. The. gases not absorbed by the washing oil in tower 22 are added to the hydrogenating gas recycled from tower 11 to the reaction vessel 1.

The following example will further illustrate the nature of the invention but the invention is not restricted thereto.

Example The liquid and vaporous products obtained by destructive hydrogenation of brown coal .at about 200 atmospheres and at about 450 centigrade are passed, together with the hydrogenating gas which has been pumped in circulation, first through a condenser, and then into a stripping vessel; here the separation of the gaseous constituents, which have not been condensed or absorbed, from the liquid occurs. The gaseous constituents are again circulated in the destructive hydrogenation process. In the remaining liquid, which consists of 15 per cent of constituents boiling at up to 200 centigrade and 70 per cent boiling at up to 325 centigrade, hydrogen, methane and its homologues and hydrogen sulphide are absorbed in a ratio corresponding to the partial pressures of these gases in the circulating gas.

The pressure on the liquid is first reduced from 200 atmospheres to about 25 atmospheres, and then secondly from about 25 atmospheres to about 1 atmosphere. By means of this releasing of pressure in stages a favorable separation of the absorbed gases is obtained since the gas obtained by reducing the pressure from about 200 atmospheres to about 25 atmospheres contains aboutw50 to 70 per cent of hydrogen, 20 to 35 per cent of hydrocarbons and 2 per cent of hydrogen sulphide, and the gas obtained in the second stage contains about 5 to 10 per cent of hydrogen, l0 to 80 per cent of hydrocarbons and 5 per cent of hydrogen sulphide. The hydrocarbons are removed from the gas obtained in the first stage by thermal decomposition or by adsorption with solvents, and the practically pure hydrogen obtained is added to the hydrogenating gas in circulation after compression to 200 atmospheres.

The circulating gas, which has not been absorbed by the condensate is kept at the same pressure and is passed through a high pressure washer filled with Raschig rings, and through which a counter current of middle oil, the greater part of which boils at between 200 and 325 centigrade, is caused to trickle. The oil, used for the washing, is employed in a circulatory cycle, and may also be subjected to fractional releasing of pressure, and if desired may be treated in vacuo in order to effect a moreV complete removal of gas.

1. In 'the process of recovering hydrocarbon gases and hydrogen 'from the vaporous products issuing from a destructive hydrogenation reaction effected under a pressure of at least 20 atmospheres which comprises subjecting said vaporous products to condensation while under the destructive hydrogenation pressure, separating the resulting condensed liquids from the uncondensed gases, recycling said uncondensed gases `to the destructive hydrogenation reaction, partially releasing the pressure on the liquid condensate to effect a separation of a portion of the normally gaseous constituents contained therein, removing the hydrocarbons present in the gaseous constituents thus obtained, recycling the remaining gaseous constituents tofthe destructive hydrogenation reaction and completely releasing the pressure on the residual condensate in one ory more stages to effect aremoval of the residual normally gaseous constituents contained vin said condensate.

`2. In the process of recovering hydrocarbon gases and hydrogen from vaporous products issuing from a destructive hydrogenation reaction effected under a pressure of at least 20 atmospheres which comprises subjecting said vaporous products to condensation while under the destructive hydrogenation pressure, separating the resulting condensed liquids from the uncondensed gases-washing the uncondensed gases to remove products other than hydrogen, recycling the hydrogen to the destructive hydrogenation reaction, partially releasing the pressure on the liquid condensate to effect a separation of normally gaseous constituents, washing said gaseous constituents to remove products other than hydrogen, recycling the hydrogen so obtained to the destructive hydrogenation reaction and completely releasing the pressure on the residual condensate to effect a removal of the residual normally gaseous constituents contained in said condensate.

3. In the process of recovering hydrocarbon gases and hydrogen from vaporous products issu- .ing from a destructive hydrogenation eiIected under a pressure of at least 20 atmospheres, which comprises subjecting said vaporous products' to condensation while under the destructive hydrogenation pressure, separating the resulting condensed liquids from the uncondensed gases. washing the uncondensed gases under high pressure to remove products other than hydrogen therefrom, recycling the hydrogen so obtained to the destructive hydrogenation reaction, partially releasing the pressure on the liquid condensate to effect a separation oi.' normally gaseous constituents therefrom, washing said constituents to remove products other than hydrogen therefrom, recompressing the hydrogen so obtained and recycling it to the destructive hydrogenation reaction and releasing the pressure on the residual condensate to eiect a removal of residual normally gaseous constituents therefrom.

4. The process as defined in claim 2 wherein the destructive hydrogenation is effected vat a pressure oi 200 atmospheres andthe pressure on the liquid condensate is iirstreduced from MATHIAS PIER. KURT 

